Use of dimethyl substituted oxymethyl cyclohexene derivatives for their repellency properties

ABSTRACT

Described is a method of repelling Musca domestica L. (Diptera:Muscida), Aedes aegypti, Culex nigripalpus, Aedes atlanticus, Culex salinarius, Aedes vexans, Culex spp., Simulium spp., Psoroferia ferox, Aedes infirmatus, Drosophila melanogaster, Coccinellidae, Anopheles crucians, Psoroferia columbiae, Culicoides spp., Aedes spp. and Haematobia irritans [L.]for a finite period of time from a three-dimensional space inhabited by said insect species consisting essentially of the step of exposing a three-dimensional space inhabited by said insect species to an effective insect species repelling concentration and quantity of at least one dimethyl substituted oxymethyl cyclohexene derivative defined according to the structure: ##STR1## wherein R 2  represents hydrogen or methyl.

This is a divisional of application Ser. No. 08/061,044, filed May 14,1993, as originally filed.

BACKGROUND OF THE INVENTION

This invention relates to the use of dimethyl substituted oxymethylcyclohexane derivatives defined according to the generic structure:##STR2## wherein Z is methylene; n is 0 or 1; each of the wavy lines isa carbon-carbon single bond or no bond; the dashed lines represents acarbon-carbon double bond or a carbon-carbon single bond; R₂, R₅, R₆, R₇and R₈ are each the same or different and each represents hydrogen ormethyl; and R₁ is hydrogen, acetyl, or methoxycarbonyl as repellents orattractants against or for: Musca domestica L.(Diptera:Muscidae), Aedesaegypti, Culex nigripalpus, Aedes atlanticus, Culex salinarius, Aedesvexans, Culex spp., Simulium spp., Psoroferia ferox, Aedes infirmatus,Drosophila melanogaster, Coccinellidae, Anopheles crucians, Psoroferiacolumbiae, Culicoides spp., Aedes spp., and Haematobia irritans [L.].

This invention also relates to the use of such compounds andcompositions of matter in insect repellent soaps, insect traps and thelike wherein the compositions of matter are used as such or incombination in control release systems with polymers such asbiodegradable polymers.

The prior art discloses a vast number of floral type fragrance materialsuseful in perfumery. However, such floral type materials in manyinstances are attractants rather than repellents for various insectsincluding the wide variety of mosquitoes which proliferate in temperate,subtropical and tropical zones as well as the wide variety of flies(e.g., Musca domestica L.(Diptera:Muscidae)) which proliferate in thetemperate and cooler climate zones. In addition, a large number ofmaterials useful in acting as insect attractants for use in insect trapsmay be effective, however, many of the more effective trapping materialshave aesthetically displeasing aromas.

The dimethyl substituted oxymethyl cyclohexane derivatives of ourinvention which are repellents and the single derivative which has beenfound surprisingly to be an insect attractant all have aestheticallypleasing aromas as disclosed, for example, in U.S. Pat. No. 5,098,886issued on Mar. 24, 1992; U.S. Pat. No. 5,100,872 issued on Mar. 31,1992; U.S. Pat. No. 4,289,146 issued on Sep. 15, 1981; and U.S. Pat. No.4,321,164 issued on Mar. 23, 1982, the specifications for which areincorporated herein by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, FLORALOL having the structure:##STR3## and ISOCYCLOGERANIOL having the structure: ##STR4## The graphsare based on experiments run for a period of one hour with six intervalsof ten minutes each using as the insect to be tested the mosquito, Aedesaegypti. The results are tabulated in Table I(A), infra.

FIG. 1B is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, FLORALOL having the structure:##STR5## and ISOCYCLOGERANIOL having the structure: ##STR6## The graphsare based on experiments run for a period of six hours with sixintervals of one hour each using as the insect to be tested themosquito, Aedes aegypti. The results are tabulated in Table I ( B),infra.

FIG. 2A is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, ISOCYCLOGERANIOL having thestructure: ##STR7## FLORALATE having the structure: ##STR8## andDIHYDROFLORALOL having the structure: ##STR9## The graphs are based onexperiments run for a period of one hour with six intervals of tenminutes each using as the insect to be tested the mosquito, Aedesaegypti. The results are tabulated in Table II(A), infra.

FIG. 2B is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, ISOCYCLOGERANIOL having thestructure: ##STR10## FLORALATE having the structure: ##STR11## andDIHYDROFLORALOL having the structure: ##STR12## The graphs are based onexperiments run for a period of eighteen hours with six intervals ofthree hours each using as the insect to be tested the mosquito, Aedesaegypti. The results are tabulated in Table II(A), infra.

FIG. 3 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air and DIHYDROFLORALOL having thestructure: ##STR13## The graphs are based on experiments run for aperiod of one hour with six intervals of ten minutes each using as theinsect to be tested the Horn fly, Haematobia irritans [L.]. The resultsare tabulated in Table III, infra.

FIG. 4 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, ISOCYCLOGERANIOL having thestructure: ##STR14## FLORALATE having the structure: ##STR15## andFLORALOL having the structure: ##STR16## The graphs are based onexperiments run for a period of one hour with six intervals of tenminutes each using as the insect to be tested the Horn fly, Haematobiairritans [L.]. The results are tabulated in Table IV, infra.

FIG. 5 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, CAMEKOL DH having the structure:##STR17## FLORALOL having the structure: ##STR18## and DIHYDROFLORALOLhaving the structure: ##STR19## The graphs are based on experiments runfor a period of one hour with six intervals of ten minutes each using asthe insect to be tested the Horn fly, Haematobia irritans [L.]. Theresults are tabulated in Table V, infra.

FIG. 6 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, FLORALATE having the structure:##STR20## and DIHYDROFLORALOL having the structure: ##STR21## The graphsare based on experiments run for a period of one hour with six intervalsof ten minutes each using as the insect to be tested the house fly,Musca domestica L.(Diptera:Muscidae). The results are tabulated in TableVI, infra.

FIG. 7 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes ) showing the relativeattractiveness or repellency of air and FLORALOL having the structure:##STR22## The graphs are based on experiments run for a period of onehour with six intervals of ten minutes each using as the insect to betested the house fly, Musca domestica L.(Diptera:Muscidae). The resultsare tabulated in Table VII, infra.

FIG. 8A is a bar graph showing the mean number of insects attracted (onthe "Y" axis) versus the treatment substance (on the "X" axis) using thesemiochemical field trap of FIG. 21 with six ports and three infra-redlight emitting diodes, showing treatment with:

(i) a 50:50 mixture of air and CO₂ ;

(ii) CAMEKOL DH having the structure: ##STR23## and (iv)ISOCYCLOGERANIOL having the structure: ##STR24## The insects measuredusing the apparatus of FIG. 21 are as follows: Culex nigripalpus;

Aedes atlanticus;

Culex salinarius

Aedes vexans;

Culex spp.;

Simulium spp.;

Psoroferia ferox;

Aedes infirmatus;

Drosophila melanogaster;

Coccinellidae;

Anopheles crucians;

Psoroferia columbiae;

Culicoides spp.; and

Aedes spp.

FIG. 8B is a bar graph showing the mean number of insects (on the "Y"axis) trapped versus treatment substance (on the "X" axis) using thesemiochemical field trap of FIG. 21 having six ports with threeinfra-red light emitting diodes. The treatment substances used are:

(i) a 50:50 mixture of air and CO₂ ;

(ii) DIHYDROFLORALOL having the structure: ##STR25## (iii)ISOCYCLOGERANIOL having the structure: ##STR26## (iv) the compoundhaving the structure: ##STR27## and (v) the compound having thestructure: ##STR28## The insects measured as to attractiveness orrepellency are as follows: Culex nigripalpus;

Aedes atlanticus;

Culex salinarius;

Aedes vexans;

Culex spp.;

Simulium spp.;

Psoroferia ferox;

Aedes infirmatus;

Drosophila melanogaster;

Coccinellidae;

Anopheles crucians;

Psoroferia columbiae;

Culicoides spp.; and

Aeries spp.

FIG. 8C is a bar graph showing the mean number of insects attracted (onthe "Y" axis) versus treatment substance (on the "X" axis) using thesemiochemical field trap of FIG. 21 (described, infra) using treatmentsubstances:

(i) a 50:50 mixture of air and CO₂ ;

(ii) FLORALOL having the structure: ##STR29## and (iii) FLORALATE havingthe structure: ##STR30## The attractancy or repellency is measured forthe following insect species:

Culex nigripalpus;

Aedes atlanticus;

Culex salinarius;

Aedes vexans;

Culex spp.;

Simulium spp.;

Psoroferia ferox;

Aedes infirmatus;

Drosophila melanogaster;

Coccinellidae;

Anopheles crucians;

Psoroferia columbiae;

Culicoides spp.; and

Aedes spp.

FIG. 9 is a cut-away side elevation schematic diagram of a screwextruder during the compounding of a resin with insect attractants orrepellents including the dimethyl substituted oxymethyl cyclohexanederivatives of our invention, while simultaneously adding foaming agentinto the hollow portion of the barrel of the extruder, and incorporatesthe pelletizing apparatus used in the pelletizing of the extruded foamedtow product produced as a result of the extrusion operation.

FIG. 10 is a cut-away side elevation view of the base section of theolfactometer apparatus of U.S. Pat. No. 5,134,892 the specification forwhich is incorporated by reference herein, used in carrying out thetesting of the attractants or repellents of our invention indicating inschematic block flow diagram form the utilization of computer-assistedefficacy measuring apparatus; but showing only an air supply entry intothe side ports of the olfactometer apparatus with the treatment agentbeing contained in a control release matrix upstream from the air supplysource.

FIG. 11 is a perspective view of an ellipsoidally shaped detergenttablet containing a solid core which includes fused foamed polymericparticles which contain insect repellents which are one of the repellingdimethyl substituted oxymethyl cyclohexane derivative-containingcompositions of our invention and, if desired, also containing anadditional polymer, e.g., polyethylene. The polymer particles may, ifdesired, also contain additional aromatizing agents.

FIG. 12 is the top view of the ellipsoidally-shaped detergent tablet ofFIG. 11.

FIG. 13 is a cut-away front view of the ellipsoidally-shaped detergenttablet of FIG. 11 in the direction of the arrows in FIG. 12.

FIG. 14 is a side-view of the ellipsoidally-shaped detergent tablet ofFIG. 11.

FIG. 15 is a perspective view of a rectangular parallelepiped-shapeddetergent tablet containing a rectangular parallelepiped-shaped corecomprising a major proportion of fused foamed polymeric particles whichcontain insect repellents (e.g., one of the repelling dimethylsubstituted oxymethyl cyclohexane derivative-containing orgeranial-containing compositions of our invention) and may or may not beadditionally aromatized and, if desired, an additional polymer which mayor may not contain insect repellent compositions and which may or maynot be additionally aromatized.

FIG. 16 is a top view of the rectangular parallelepiped-shaped detergenttablet of FIG. 15.

FIG. 17 is a cut-away front view of the rectangularparallelepiped-shaped tablet of FIG. 15 looking in the direction of thearrows in FIG. 16.

FIG. 18 is a perspective view of an ellipsoidally-shaped detergenttablet containing a hollow insect repellent agent (and if desired, anadditional aromatizing agent) containing core which includes fusedfoamed polymeric particles containing insect repellent and if desiredadditional aromatizing agent or, in the alternative, a hollow core offused foamed polymer wherein the insect repellent which is also an aromaimparting agent (and if desired, an additional aroma imparting agent) isin the solid polymer and not in the void of the plastic core.

FIG. 19 is a top view of the ellipsoidally-shaped detergent tablet ofFIG. 18.

FIG. 20 is a front cut-away view of the ellipsoidally-shaped detergenttablet of FIG. 18 looking in the direction of the arrows in FIG. 19, thecore thereof being hollow and either containing an insect repellentmaterial of our invention (and if desired, an additional aroma impartingliquid) or in the alternative being a hollow core wherein the insectrepellent material of our invention (and if desired, the additionalaroma imparting material) is in the solid fused foamed polymericparticles which make up the core and wherein the void does not containanything.

FIG. 21 is a perspective view of the semiochemical field trap fortesting the attractiveness or repellency for blood feeding arthropodsusing the dimethyl substituted oxymethyl cyclohexane derivative and/orgeranial-containing repellency composition of our invention or theattractant of our invention which is the compound having the structure:##STR31##

The semiochemical field trap is described in detail in U.S. applicationSer. No. 887,138 filed on May 22, 1992, now U.S. Pat. No. 5,228,233 thespecification for which is incorporated herein by reference.

FIG. 22 is a bar graph showing the mean number of feeding contacts (onthe "Y" axis) versus the particular treatment substance (on the "X"axis) for air, FLORALATE having the structure: ##STR32## and geranialhaving the structure: ##STR33## for a mean feeding contact time of onehour.

FIG. 23 is a bar graph showing the mean number of feeding contacts (onthe "Y" axis) versus the particular treatment substance (on the "X"axis) for air, FLORALATE having the structure: ##STR34## and geranialhaving the structure: ##STR35## for a mean 2-6 hour feeding contacttime.

SUMMARY OF THE INVENTION

This invention relates to the use of dimethyl substituted oxymethylcyclohexane derivatives defined according to the structure: ##STR36##and geranial having the structure: ##STR37## (wherein Z is methylene; nis 0 or 1; each of the wavy lines represents a carbon-carbon single bondor no bond (when n is 0); the dashed line represents a carbon-carbondouble bond or a carbon-carbon single bond; each of R₂, R₅, R₆, R₇ andR₈ represent hydrogen or methyl; and R₁ is hydrogen acetyl orethoxycarbonyl as insect repellents against house flies (Musca domesticaL.(Diptera:Muscidae)), mosquitoes including those set forth on thefollowing species list:

Culex nigripalpus;

Aedes atlanticus;

Culex salinarius;

Aedes vexans;

Culex spp.;

Simulium spp.;

Psoroferia ferox;

Aedes infirmatus;

Drosophila melanogaster;

Coccinellidae;

Anopheles crucians;

Psoroferia columbiae;

Culicoides spp.; and

Aedes spp.

and the Horn fly, Haematobia irritans [L.].

This invention also use relates to the of the compound having thestructure: ##STR38## as an attractant for the insect species: Culexnigripalpus;

Aedes atlanticus;

Culex salinarius;

Aedes vexans;

Culex spp.;

Simulium spp.;

Psoroferia ferox;

Aedes infirmatus;

Drosophila melanogaster;

Coccinellidae;

Anopheles crucians;

Psoroferia columbiae;

Culicoides spp.; and

Aedes spp.

Specific examples of the dimethyl substituted oxymethyl cyclohexanederivatives useful in the practice of our invention are those having thefollowing structures: ##STR39##

Our invention also relates to the use of the foregoing insect repellentcompositions in personal soap compositions, for example, the insectrepellent soap composition described in U.S. Pat. No. 4,707,496 issuedon Nov. 17, 1987, the specification for which is incorporated byreference herein. Thus, in applying the teachings of U.S. Pat. No.4,707,496 to our invention, a topical insect repellent soap compositionand a method of protection using such a composition is described wherethe insect repellent soap composition comprises:

(i) from 63.0 up to 99.5% by weight of a soap mixture containing from4.1 to 7% by weight of a soap of caprylic acid, from 3.8 to 7% of a soapof capric acid, from 32.1 to 45% of a soap of lauric acid, from 12 to17.5% by weight of a soap of myristic acid, from 5.0 up to 10% by weightof a soap of palmitic acid, from 1.6% to 3% by weight of a soap ofstearic acid, from 3.5 to 5% by weight of a soap of oleic acid and from0.9 to 5% by weight of a soap of linoleic acid;

(ii) from 0.1 up to 2% by weight of C₈ -C₁₈ is straight chain fattyacids.

(iii) from 10 up to 30% by weight of one of the dimethyl substitutedoxymethyl cyclohexane derivative-containing or geranial-containingcompositions of our invention as set forth, supra, and

(iv) from 0.2 up to 5% by weight of an effective residual insecticide asdescribed in U.S. Pat. No. 4,707,496.

Other insect repellent soaps can be produced by adding an appropriatedimethyl substituted oxymethyl cyclohexane derivative-containing orgeranial-containing composition of our invention to one or more of thecompositions described and claimed in U.S. Pat. No. 4,453,909 issued onJun. 12, 1984 and U.S. Pat. No. 4,438,010 the specifications for whichare incorporated by reference herein. Described in said U.S. Pat. No.4,453,909 and U.S. Pat. No. 4,438,010 is a process for making a tabletof saop containing a perfume containing core, hollow or solid fabricatedfrom a hard plastic material either thermosetting or thermoplastic. Thesoap from the resulting composite tablet is useable until the core iswashed clean and contains functional ingredients, e.g., the repellentsdescribed, supra, and optionally, aromatizing agent until the core iswashed clean. This obviates the wastage of soap which normally occurs asa conventional soap tablet becomes very thin on use and at the same timegives rise to a continuously functional ingredient containing soap,(e.g., repellent and optionally aromatizing agent) tablet. Thus, thisinvention also relates to detergent bars having a plastic corecontaining an appropriate dimethyl substituted oxymethyl cyclohexanederivative-containing or geranial-containing composition and optionally,an additional perfume. More particularly, this invention relates todetergent bars intended for conventional toilet soap uses either as handsoaps or bath or shower soaps which are elastic or inelastic in naturebut which contain a solid plastic core containing insect repellent andoptionally perfume giving them unique properties which alleviate wastagethereof and causes the environment surrounding the soap on use thereofto be both insect repellent and optionally aromatized in anaesthetically pleasing manner.

Yet another aspect of our invention relates to the use of the dimethylsubstituted oxymethyl cyclohexane derivative-containing orgeranial-containing repellents of our invention taken further incombination with N-(methyl toluyl)-methyl piperidines defined accordingto the structure: ##STR40## as described in U.S. Pat. No. 3,463,855issued on Aug. 26, 1969, the specification for which is incorporated byreference herein. The compounds defined according to the structure:##STR41## include: N-(meta-toluyl)-2-methylpiperidine;

N-(meta-toluyl)-3-methylpiperidine; and

N-(meta-toluyl)-4-methylpiperidine.

The proportions of compounds defined according to the structure:##STR42## to the appropriate dimethyl substituted oxymethyl cyclohexanederivative or geranial-containing composition described, supra, arebetween about 1 part N-(meta-toluyl) methylpiperidine:99 partsappropriate dimethyl substituted oxymethyl cyclohexane derivative orgeranial-containing composition of our invention down to 99 partsappropriate dimethyl substituted oxymethyl cyclohexane derivative orgeranial-containing composition of our invention: 1 partN-(meta-toluyl)-methylpiperidines.

In addition, the compositions useful in repelling insects of ourinvention can also contain 1-nonen-3-ol described and claimed in U.S.Pat. Nos. 4,693,890 and 4,759,228 issued on Jul. 26, 1988, thespecifications for which are incorporated by reference herein, The ratioof 1-nonen-3-ol:appropriate dimethyl substituted oxymethyl cyclohexanederivative or geranial-containing composition of our invention useful inrepellent compositions may vary from about 1 part 1-nonen-3-ol:99 partsappropriate dimethyl substituted oxymethyl cyclohexane derivative orgeranial-containing composition of our invention down to 99 parts1-nonen-3-ol:1 part appropriate dimethyl substituted oxymethylcyclohexane derivative or geranial-containing composition of ourinvention.

In addition to the soap fabrication, another aspect of our inventionrelates to the formation of repelling articles containing theappropriate dimethyl substituted oxymethyl cyclohexane derivative orgeranial-containing compositions of our invention, that is, articlesuseful for repelling house flies (Musca domestica L.(Diptera:Muscidae))or the mosquitoes (Aedes aegypti) or other insect species:

Culex nigripalpus;

Aedes atlanticus;

Culex salinarius;

Aedes vexans;

Culex spp.;

Simulium spp.;

Psoroferia ferox;

Aedes infirmatus;

Drosophila melanogaster;

Coccinellidae;

Anopheles crucians;

Psoroferia columbiae;

Culicoides spp.; and

Aedes spp.

or the Horn fly (Haematobia irritans [L.]) in combination withcompatible polymers which may or may not be biodegradable (for example,high density polyethylene or low density polyethylene, or biodegradablepolymers such as biodegradable thermoplastic polyurethanes as disclosedin Japan Kokai Tokyo Koho 92/13710 (abstracted at Chem. Abstracts Volume116:236374q), biodegradable ethylene polymers having ester linkages inthe main chain such as that disclosed by Japan Kokai Tokyo Koho 92/50224(abstracted at Chem. Abstracts Volume 116:236397z), biodegradableethylene polymers disclosed by Japan Kokai Tokyo Koho 92/50225(abstracted at Chem. Abstracts Volume 116:126398a) and poly(epsiloncaprolactone) homopolymers and compositions containing same as disclosedin U.S. Pat. Nos. 4,496,467; 4,469,613 and 4,548,764 the specificationsfor which are incorporated herein by reference). Thus, another aspect ofour invention provides a process for forming appropriate dimethylsubstituted oxymethyl cyclohexane derivative or geranial-containingcompositions containing polymeric particles such as foamed polymericpellets which include a relatively high concentration of the appropriatedimethyl substituted oxymethyl cyclohexane derivative orgeranial-containing compositions of our invention as defined, supra.

Thus, another aspect of our invention relates to the formation ofappropriate dimethyl substituted oxymethyl cyclohexane derivative orgeranial-containing polymeric pellets by means of introduction into asingle or twin screw extruder, in series, a thermoplastic polymerfollowed by the appropriate dimethyl substituted oxymethyl cyclohexanederivative or geranial-containing composition of our invention which iscompatible with the thermoplastic polymer, in turn, (optionally)followed by introduction of gaseous blowing agent or blowing agent whichwill produce a gas which is inert to the polymer and to the appropriatedimethyl substituted oxymethyl cyclohexane derivative-containing orgeranial-containing composition previously introduced into the extruder.

The advantages of using a foamed polymeric particle are multiple, towit:

(i) improved handling;

(ii) greater retention of the appropriate dimethyl substituted oxymethylcyclohexane derivative-containing or geranial-containing compositionwhen not in use; and

(iii) greater length of time during which the release of the appropriatedimethyl substituted oxymethyl cyclohexane derivative-containing orgeranial-containing composition of our invention from the polymer is at"steady state" or "0 order".

The nature of the extruder utilized in the process of our invention toform the appropriate dimethyl substituted oxymethyl cyclohexanederivative-containing or geranial-containing composition-containingpolymer particles of our invention may be either single screw or doublescrew. Thus, the types of extruder that can be used are disclosed atpages 246-267 and 332-349 of the Modern Plastics Encylopedia, 1982-1983,published by the McGraw-Hill Publishing Company, the disclosure of whichis incorporated by reference herein. More specifically, examples ofextruders which are useable in carrying out one or more of the processesof our invention (with modification for introduction of the appropriatedimethyl substituted oxymethyl cyclohexane derivative-containing orgeranial-containing compositions of our invention) downstream from theintroduction of the polymer and with further modification that thegaseous blowing agent is introduced still further downstream from thepoint of introduction of the appropriate dimethyl substituted oxymethylcyclohexane derivative-containing or geranial-containing compositions ofour invention are as follows:

1. The Welex "Super Twinch" 3.5" extruder manufactured by WelexIncorporated, 850 Jolly Road, Blue Bell, Pa. 19422;

2. Krauss-Maffei twin screw extruder manufactured by the Krauss-MaffeiCorporation/Extruder Division, 3629 West 30th Street South, Wichita,Kans. 67277;

3. Modified Sterling model 4000 and 5000 series extruder manufactured bySterling Extruder Corporation of 901 Durham Avenue, South Plainfield,N.J.;

4. CRT ("Counter-Rotating Tangential"), Twin Screw Extruder manufacturedby Welding Engineers, Inc. of King of Prussia, Pa. 19406;

5. The Leistritz Twin Screw Dispersion Compounder manufactured by theAmerican Leistritz Extruder Corporation of 198 U.S. Route 206 South,Somerville, N.J. 08876;

6. The ZSK Twin Screw Co-Rotating Extruder manufactured by the Werner &Pfleiderer Corporation of 663 East Crescent Avenue, Ramsey, N.J. 07446;

7. The Farrel Extruder manufactured by Farrel Connecticut Division,Emhart Machinery Group, Ansonia, Conn. 06401;

8. The MPC/V Baker Perkins Twin Screw Extruder manufactured by the BakerPerkins Inc. Chemical Machinery Division of Saginaw, Mich. 48601; and

9. The Berstorff single screw, twin screw, or foam extrusion equipmentmanufactured by Berstorff Corporation, P. O. Box 240357, 8200-A ArrowingBlvd., Charlotte, N.C. 28224.

In producing the appropriate dimethyl substituted oxymethyl cyclohexanederivative-containing or geranial-containing composition-containingpolymer particles of our invention, various polymers may be utilized,for example, low density polyethylene, high density polyethylene,polypropylene, the co-polymer of ethylene and vinyl acetate, andpolyvinyl chloride. More specifically, the polymers used in the practiceof our invention may be co-polymers of ethylene and a polar vinylmonomer selected from (a) vinyl acetate; (b) ethyl acrylate; (c) methylacrylate; (d) butyl acrylate and (e) acrylic acid including thehydrolyzed co-polymer of ethylene and vinyl acetate. Preferredco-polymers are ethylene/vinyl acetate with about, 9 to 60% vinylacetate and ethylene/ethyl acrylate with about 6 to 18% ethyl acrylate.

Resins of the type disclosed for use as co-polymers are commericallyavailable in the molding powder form; for example, ethylene vinylacetate co-polymers are marketed by the E. I. duPont Nemours Companyunder the tradename "ELVAX® and by the Arco Polymer Division under thetrademark "DYLAND® and by the Exxon Corporation of Linden, N.J. underthe trademark "DEXXON®. Ethylene/ethyl acrylate co-polymers are marketedby Union Carbide Corporation under the trademark "EEA RESIN®.

The polymer is added to the single screw or twin screw extruder at afeed rate in the range of from about 80 up to about 300 pounds per hourwhile maintaining the temperature of the screw extruder between about160° C. and about 240° C. If the polymer or co-polymer powder is addedto the extruder at a reference "barrel segment" then the appropriatedimethyl substituted oxymethyl cyclohexane derivative-containing orgeranial-containing composition of our invention is added to theextruder under pressure downstream from the retention point of thepolymer at one or more of "barrel segments" (S-2, S-3, S-5, S-6, S-7,S-8 or S-9) (referring to FIG. 9 briefly described, supra, and describedin detail, infra).

The proportion of the appropriate dimethyl substituted oxymethylcyclohexane derivative-containing or geranial-containing composition(taken further together with other insect repelling materials, ifdesired) to resin can vary from small but effective amounts on the orderof about 1% of the weight of the resin body up about 45% by weight ofthe resin body. In general, it is preferred to use between about 5% upto about 30% based on the weight of the resin body of insect repellentcomposition of our invention. This is an optimum amount balancing theproportion of the insect repellent composition of our invention againstthe time period over which the article emits the insect repellentcomposition and against the tendency of the components of the insectrepellent composition to oil out either individually or in combination.This "oiling out" is specifically avoided as a result of the use of thefoaming agent discussed, infra.

Various polymers are useful in the practice of our invention. Specificexamples of polymers useful in the practice of our invention are asfollows:

(a) DYLAN® brand of low density polyethylene DYLAN® is a trademark ownedby the Atlantic Richfield Company of Los Angeles, Calif.;

(b) DYLITE® of expandable polystyrene composition, DYLITE® is atrademark of Atlantic Richfield Company of Los Angeles, Calif.;

(c) SUPER DYLAN® is a trademark of the Atlantic Richfield Company of LosAngeles, Calif.;

(d) Blended polyethylene and carbon black as specifically taught in U.S.Pat. No. 4,369,267 issued on Jan. 18, 1983, the specification for whichis incorporated by reference herein;

(e) Polystyrene as disclosed in U.S. Pat. No. 4,369,227 issued on Jan.18, 1983, the specification for which is incorporated by referenceherein;

(f) Polyene/alpha-olefin as exemplified and disclosed in U.S. Pat. No.4,369,291, the specification for which is incorporated by referenceherein;

(g) Poly-alpha-olefins as exemplified in Canadian Letters Patent No.1,137,069 issued on Dec. 7, 1982, the specification for which isincorporated by reference herein;

(h) Polymeric compositions as disclosed in Canadian Letters Patent No.1,137,068 issued on Dec. 7, 1982, the specification for which isincorporated by reference herein;

(i) Poly-alpha-olefins disclosed in Canadian Letters Patent No.1,137,067, the specification for which is incorporated by referenceherein;

(j) Polyolefins described in Canadian Letters Patent No. 1,137,066, thespecification for which is incorporated by reference herein;

(k) Polyethylene oxides as disclosed in Canadian Letters Patent No.1,137,065 issued on Dec. 7, 1982, the specification for which isincorporated by reference herein;

(l) Olefin polymers and co-polymers as disclosed in Canadian LettersPatent No. 1,139,737, the disclosure of which is incorporated byreference herein. Canadian Letters Patent No. 1,139,737 was issued onJan. 18, 1983;

(m) Polyolefins disclosed in Canadian Letters Patent No. 1,139,738, thedisclosure of which is incorporated by reference herein. CanadianLetters Patent No. 1,139,738 was issued on Jan. 18, 1983;

(n) Chlorinated PVC as disclosed in Polymer 1982, 23 (7 ,Suppl.), 1051-6abstracted at Chem. Abstracts Volume 97:14550y, 1982;

(o) Polyepsilon caprolactone co-polymers made by means of alcoholinitiated polymerization as disclosed in J. Polym. Sci. Polym. Chem. Ed.1982, 20(2), pages 319-26, abstracted at Chem. Abstracts, Volume96:123625x, 1982;

(p) Styrene acrylonitrile co-polymers as disclosed in Diss. AbstractsInt. B, 1982, 42(8), 3346 and abstracted at Chem. Abstractss Volume96:14 3770n, (1982);

(q) Co-polymers of epsilon caprolactone with 1,4-butane diol asdisclosed at Kauch Rezine, 1982, (2), 8-9, abstracted at Chem. AbstractsVolume 96:182506g (1982);

(r) Polyesters as disclosed in U.S. Pat. No. 4,326,010, thespecification for which is incorporated by reference herein;

(s) Chlorinated polyethylene as disclosed by Belorgey, et al, J. Polym.Sci. Plym. Ed. 1982, 20(2), 191-203;

(t) Plasticized polyepsilon caprolactone co-polymers containing dimethylphthalate plasticizers as set forth in Japanese Patent No. J81/147844,abstracted at Chem. Abstracts Volume 96:69984y (1982), the specificationfor which is incorporated by reference herein;

(u) Maleic anhydride modified adducts of polyepsilson caprolactonepolyols and ethylenically unsaturated monomer as disclosed in U.S. Pat.No. 4,137,279 issued on Jan. 30, 1979, the specification for which isincorporated by reference herein;

(v) Polyurethane polymers having lactone backbones as disclosed in U.S.Pat. No. 4,156,067 issued on May 22, 1979, the disclosure of which isincorporated by reference herein;

(w) Polyurethane polyether resins wherein the resin is obtained byreacting a polyfunctional lactone with a long chain polyalkylene dioland a urethane precursor as disclosed in U.S. Pat. No. 4,355,550 issuedon Mar. 10, 1981, the disclosure of which is incorporated by referenceherein; and

(x) Resins having polyurethane backbones as disclosed in U.S. Pat. No.3,975,350 issued on Aug. 17, 1976, the disclosure of which isincorporated by reference herein.

Examples of poly(epsilon caprolactone) homopolymers as set forth, forexample, in U.S. Pat. No. 4,496,467 are those having the structures:##STR43## wherein n represents an integer of from about 500 up to about1200 with the proviso that the average "n" varies from about 600 up toabout 800.

Downstream from the addition point of the dimethyl substituted oxymethylcyclohexane derivative-containing or geranial-containing compositions ofour invention taken alone or taken together with other insect repellentagents and fragrance materials, optionally, the gaseous or liquidcontaining blowing agent may be added (e.g., at "barrel segments" (S-5,S-6, S-7, S-8, S-9 or S-10) using the polymer addition "barrel segment"as a refrence "barrel segment" S-1. Examples of the gaseous blowingagents are carbon dioxide, nitrogen, mixtures of nitrogen and carbondioxide in proportions of from 1 up to 99% by volume nitrogen and from99 down to 1% by volume carbon dioxide, helium, mixtures of helium andnitrogen, mixtures of helium and carbon dioxide and other gases whichare inert at the temperature and pressure of the polymer at the time ofthe extrusion operation. Thus, gas containing oxygen or other reactivegases, e.g., hydrogen, should be avoided. The pressure of the gasblowing agent being added to the extruder at the point of addition mayvary from about 80 to about 150 psig. Higher pressures may be usedwithout adversely affecting the usefulness of the foamed insectrepellent composition-containing particle.

The feed rate range of insect repellent compositions which contain butwhich are not limited to the dimethyl substituted oxymethyl cyclohexanederivative-containing and/or geranial-containing compositions of ourinvention, may be between about 0.5% up to about 45% by weight of thepolymer. It must be emphasized at this point that the insect repellentcomposition of our invention which are the dimethyl substitutedoxymethyl cyclohexane derivative-containing compositions and/or thegeranial-containing compositions of our invention are in and ofthemselves aromatizing materials. However, the maximum quantity of thecombination of other aromatizing materials and the appropriate dimethylsubstituted oxymethyl cyclohexane derivative-containing and/orgeranial-containing compositions of our invention is 45%.

The dies of the extruder may create rod, sheet, film or ribbon. Theresulting product may then, if desired, be pelletized to form insectrepellent composition-containing polymer particles or the ribbon may beused "as is" as an insect repellent-containing polymeric article ofmanufacture itself.

In addition to the optional gaseous blowing agents (which arenecessarily "inert" gases), blowing agents may be added at the samepoint on the extruder which will create gaseous voids in the insectrepellent-containing polymer articles of our invention and these"blowing agents" are well known to one having ordinary skill in the art.Examples of such non-gaseous containing materials which yield gases onadmixture with the polymer in the extruder but which are still insert tothe insect repellent (or attractant in the event of formulation ofmicroporous polymeric particles containing the compound having thestructure: ##STR44## for use in insect traps as the case may be) are asfollows: (i) Under high pressure, ethylene, methane, propane, butane,propylene, methyl chloride, methyl bromide, vinyl chloride and methylenedichloride as more specifically described in U.S. Pat. No. 2,387,730,the specification for which is incorporated by reference herein;

(ii) Ordinarily liquid material such as n-pentane, isopentane,cyclopentane, hexane and petroleum ether fractions or halogenhydrocarbons such as CFCl₃, CF₂ Cl₂, CH₃ Cl, CH₂ Cl₂ separately or inadmixture with one another as set forth in U.S. Pat. No. 3,758,425,column 4, line 1-5, the specification for which is incorporated byreference herein;

(iii) Dichlorotetrafluoromethane, tetramethylmethane,monochlorodifluoromethane, dichlorodifluoromethane, anddichlorotetrafluoromethane as described in U.S. Pat. Nos. 2,948,664 and2,948,665 issued on Aug. 9, 1990, the specification for which isincorporated by reference herein; and

(iv) Azo bis(formamide), diazoaminobenzene; N,N-dinitrosopentamethylenetetramine; N,N-dimethyl, N,N-dinitrosoterephthalamide;p,p'-oxy-bis-(benzen sulfonyl semicarbazide); aza bis-(isobutyronitrile)p,p'-oxy-bis(benzene sulfonyl hydrazide); p,p'-diphenyl-bis(sulfonylhydrazide); benzene-sulfonyl hydrazide; m-benzene-bis(sulfonylhydrazide) as more specifically described in U.S. Pat. No. 3,298,975issued on Jan. 17, 1967, the specification for which is incorporated byreference herein.

The resulting extruded (and, if desired, pelletized) material may thenbe, for example, injection molded to form a useful article. Suchinjection molding can be carried out in accordance with the procedure asset forth in U.S. Pat. No. 3,268,636 issued on Aug. 23, 1966, thespecification for which is incorporated by reference herein.

In addition, our invention relates to candle body materials which on useare both insect repellent and perfuming which contain the appropriatedimethyl substituted oxymethyl cyclohexane derivative-containing and/orgeranial-containing compositions of our invention and, if desired, otherinsect repellent materials including, for example, at least one of thecompounds having the structure: ##STR45## in order to repel house flies(Musca domestica L.(Diptera:Muscidae)) and/or the mosquitoes, Aedesaegypti, and/or the insect species:

Culex nigripalpus;

Aedes atlanticus;

Culex salinarius;

Aedes vexans;

Culex spp.;

Simulium spp.;

Psoroferia ferox;

Aedes infirmatus;

Drosophila melanogaster;

Coccinellidae;

Anopheles crucians;

Psoroferia columbiae;

Culicoides spp.; and

Aedes spp.

and/or the Horn fly, Haematobia irritans [L.].

The house fly, Horn fly and mosquito-repellent-perfuming compositionswhich form part of the candle body materials are within the followingspecifications:

(I) from 5 up to 100% by weight of an efficacious perfuming/insectrepellent composition containing an appropriate dimethyl substitutedoxymethyl cyclohexane derivative-containing and/or geranial-containingcomposition of our invention; and

(II) from 0 up to 95% by weight of an additional standard perfumingsubstance (non-insect repellent or insect repellent) which may includebut is not limited to:

1-nonen-3-ol;

1-octen-4-ol;

alpha-damascone;

beta-damascone;

delta-damascone;

trans,trans delta-damascone;

methyl jasmonate;

dihydromethyl jasmonate;

the schiff base of vanillin and methyl anthranilate;

the schiff base of ethyl vanillin and methyl anthranilate;

vanillin; and

ethyl vanillin.

The foregoing formula may require a solubilizing agent, e.g., the methylester of dihydroabietic acid (commerical name: HERCOLYN D®), benzylbenzoate, isopropyl myristate and/or C₁₂ -C₁₄ isoparaffin hydrocarbons.

The candle base composition can be standard paraffin wax, or it can betransparent or pastel shaded as more particularly described in U.S. Pat.No. 3,615,289 issued on Oct. 26, 1971 (the disclosure of which isincorporated by reference herein) and wherein the candle body comprisesas the basic components a mixture of:

(i) a thermoplastic polyamide resin formed from linoleic acidpolymerized with a polyamine compound;

(ii) an alkanol amide or alkanol amine; and

(iii) a stearic acid compound.

The weight ratio of candle body:insect repellent/perfumant substance orour invention may vary from about 0.8% up to about 10% with a range offrom about 0.8% up to about 2.0% being preferred when no additionalnon-insect repelling perfume oil is used in conjunction with theappropriate dimethyl substituted oxymethyl cyclohexanederivative-containing or geranial-containing composition of ourinvention; and with a range of from about 1.5% up to about 10% by weightof the overall composition being preferred when an additional non-insectrepelling perfume oil is used in conjunction with the appropriatedimethyl substituted oxymethyl cyclohexane derivative-containing and/orgeranial-containing composition of our invention.

Specifically, the polyamide may be a "VERSAMID® resin which is athermoplastic condensation product of polymerized linoleic acid withvarious polyamine compounds such as ethylene diamine, ethylene triamineand the like. Specific "VERSAMID® compounds are "VERSAMID® 900","VERSAMID® 930", "VERSAMID® 940", "VERSAMID® 948", "VERSAMID® 950" and"VERSAMID® 1635". These compounds are products of the Henkel ChemicalCorporation of Minneapolis, Minn.

Another substance required in the clear candle composition consists ofabout 20-55% by weight of an alkanol amine or alkanol amide prepared bythe reaction of a fatty acid ester and amine whereby the ester and theamine are in substantially equal proportions, for example, compoundssuch as BARLOL® 12C2 (manufactured by the Baroid Chemical Company) amonoalkyl diethanolamine having 8 to 18% carbon atoms in the alkylchain. A third component of the clear plastic candle compositioncomprises one or more stearic acid esters or a mixture of stearic acidesters and stearic acid. These esters include such compounds asisopropyl isostearate, butyl stearate and hexadecyl stearate. Thesestearic acid compounds serve as stabilizing agents which permit theready incorporation of the insect repellent/perfumant compositions ofour invention up to a level of approximately 5% (total proportion ofperfume oil-insect repellent composition). They are carriers for theperfumant/insect repellent and may be used in a proportion of between 1and 50% by weight of the composition although the preferable range isbetween 20 to 30%. In this connection it is possible to use up to about10% by weight of a perfumant/insect repellent if part of the formula isreplaced by the material "NEVEX® 100", a product which is acoumarin-indene copolymer resin of very little unsaturation manufacturedby the Neville Chemical Company.

Rather than being a crystalline paraffin wax the candle base of ourinvention may be an oil gel that has as its base a light mineral oil, aninexpensive natural oil or a combination of such oils which oil gel hasa non-greasy surface and feel and sufficient rigidity to beself-supporting at room temperature. Such a gel is disclosed in U.S.Pat. No. 3,645,705 issued on Feb. 29, 1972, the disclosure of which isincorporated by reference herein. Such compositions of matter include:

(a) from about 35% up to about 85% by weight of an oil which is normallyliquid at room temperature chosen from the group consisting of lightmineral oils and natural oils having iodine values substantially withinthe range of 40-135;

(b) from about 7% up to about 40% by weight of a long chain polyamidehaving a molecular weight substantially within the range of 6000-9000and a softening point substantially within the range of 18° C.-48° C.;and

(c) from about 7% up to about 30% of an alcohol selected from the groupconsisting of 8 to 12 carbon primary alcohols.

Similarly, when used in insect traps, the attractant of our inventionhaving the structure: ##STR46## can be used in the same polymers as therepellents. Thus, for example, our invention contemplates the attractanthaving the structure: ##STR47## (at a level of from about 1% up to about45% by weight of the polymer composition) imbedded in the interstices ofa microporous polymer which may be one of the polymers as set forth,supra.

Furthermore, the insect attractant-containing polymers of our inventionmay be insect attractant-containing biodegradable polymers as set forth,supra.

The dimethyl substituted oxymethyl cyclohexane derivatives of ourinvention may be in the form of racemic mixtures or they may be in theform of sterioisomers. Thus, for example, representations of suchsterioisomers are representations having the following structures:##STR48## wherein R₁ is methyl or ethyl and R₂ is hydrogen or methyl.

DETAILED DESCRIPTION OF THE DRAWINGS

The data set forth in FIGS. 1A, 1B, 2A, 2B, 3, 4, 5, 6, 7, 8, 8A, 8B,8C, 22 and 23 were determined using the olfactometer of FIG. 10 and theinsect trap of FIG. 21.

Referring to the olfactometer of FIG. 10, said olfactometer is describedin detail in U.S. Pat. No. 5,118,711 issued on Jun. 2, 1992, thespecification for which is incorporated by reference herein.

Referring to FIG. 10, air supply source 3634 provides air to mixingstation 3636 wherein the air is mixed with treatment agent fromtreatment agent source 3635 (source of, for example, the repellentcomposition which is an appropriate dimethyl substituted oxymethylcyclohexane derivative-containing and/or geranial-containingcomposition) or the attractant having the structure: ##STR49## Theresulting mixture passes through tube 3636g and enters the apparatusthrough the side portals. The entry is through a spacer plate and abovebase plate 3625. The entry of the air-treatment agent is in a directionparallel to the surface of base plate 3625. Thus, the base plate 3625 isseparated from spacer plate 3629 for the air-treatment agent (e.g., theappropriate dimethyl substituted oxymethyl cyclohexanederivative-containing and/or geranial-containing composition of ourinvention).

Air exits through line 3633a using exhaust fan 3633. The air exit isindicated by reference numeral 3537.

Simultaneously, with the supplying of air and treatment agent frommixing station 3636, light is supplied from beneath the enclosed insectfeeding and/or stimulating means through light guides 3652, from lightsource 3551 which is powered by electric power supply 3550 marketed byRADIO SHACK® Division of Tandy Corporation of Fort Worth, Tex. 76102under the trademark ARCHER®, Catalog No. 276-228 ("1.0 mm opticalplastic fiber length 5 meter"). An example of light source 3551 isKRATOS Monochromatic Illuminator GM 100 Miniature VIS-IR GratingMonochromator (Model No. GM 100-1, GM 100-2, GM 100-3 or GM 100-4) asmanufactured by KRATOS Analytical Instruments Corporation, 170 WilliamsDrive, Ramsey, N.J. 07446. Another light supply source is the KRATOS GM200 Double Grating Monochromator. Another example of a useful lightsource is the KRATOS GM 252 High Intensity Grating Monochromator. Thebase plate 3625 is also separated from the spacer plate 3629 for thelight guides 3652 whereby the light guides 3652 are held in place in thebase plate 3625 whereby the light (or other forms of radiation) isdirected in a direction perpendicular to the electrical sensor element3610. Air supply source from location 3634 and treatment agent fromlocation 3635 is mixed at mixing station 3636 whereupon treatment agentand air in admixture is passed through lines 3636a and 3636g throughportals located in the spacer element 3628 in a direction along adirectional vector parallel to the electrical sensing element 3610 heldin place by holders 3610a and 3610b. The electrical sensing elements arelocated directly below the horizontally positioned insect feeding and/orstimulating microporous substantially planar lamina 3670 which is heldin place by ring 3660 located on spacer plate 3629 spaced from the baseplate 3625 by spacer ring 3628. It should be noted that the spacer plate3629, spacer ring 3628 and base plate 3625 enclose the entire "enclosedinsect feeding and/or stimulating means" which have controlled limitedaccess to the external environment surrounding the apparatus and inwhich the insects to be tested, e.g., mosquitoes, Horn flies or houseflies are placed.

The insect attractant quantitative detecting means made up of wires 3699(the entire grid being denoted using reference numeral 3610) is locatedimmediately beneath the porous membrane 3670, the outer surface of whichcontains a feeding stimulant composition or stimulant composition forinsects (for example, agar). Immersed in the feeding stimulatecomposition or stimulant composition for insects (e.g., agar) iselectrode 3679 connected to wire 3619 which connects with either wire3619a or 3619b which is connected to the grid wires 3699 (which make upthe insect attractant quantitative detecting means located immediatelybelow lamina 3670).

As stated, supra, the sensor causes an electrical impulse caused by thepressure of the insect's landing to proceed through wires 3619a and3619b to an electrically biased differential amplifier 3639 (usingelectrical power supply 3539) also connected to wire 3619c which isconnected to the electrode 3679 which is immersed in the feedingstimulant composition or stimulant for the insect and then to amulti-channel A.C. converter 3523. Converter 3523 is associated withprogram tape storage 3524, printer 3520 and data link to digitalcomputer 3521. Differential amplifer 3639 is connected in series toelectrical bias for pseudo host 3669 which in turn is connected to wire3619 which in turn is connected to the electrode 3679 immersed in theinsect stimulant composition located on the surface of porous lamina3670.

Referring to the testing apparatus, the semiochemical field trap 1000for blood feeding arthopods, field trap 1000 is located in a three-spacewith axes perpendicular to one another. The semiochemical field trap1000 is shown in perspective view in FIG. 21 comprising:

(1) an upright vertically disposed housing;

(2) extending outwardly from the housing a plurality of horizontallydisposed hollow housings 116a and 116b which have contained thereininsect sticky traps;

(3) air 138 and/or carbon dioxide supply means 134, 136 for supplyingair and/or carbon dioxide into the vertical hollow housing and thenthrough the plurality of horizontally disposed hollow housings 116a and116b; and

(4) at least one power supply means for energizing radiation meanslocated on the vertical hollow housing

whereby on engagement of the power supply means with the radiation meansand operation of the air 138 and/or carbon dioxide supply means 134,136, arthropods in the vicinity of the trap are attracted by theactivated radiation means and the gas emanating from the horizontallydisposed hollow housing 116a to a location so close to the trap 1000that in the event that an attracting semiochemical located in thehousings 116a and 116b is detected by at least one of the arthropods, atleast one of the arthropods will enter the inner void of thehorizontally disposed hollow housings 116a and 116b counter current thegas stream emanating therefrom and remain permanently entrapped therein.

The semiochemical field trap 1000 of FIG. 21 is disclosed in detail inU.S. application Ser. No. 887,138 filed on May 22, 1992, thespecification for which is incorporated by reference herein.

FIG. 1A is a series of graphs depicted in three-dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, ISOCYCLOGERANIOL having thestructure: ##STR50## and FLORALOL having the structure: ##STR51## withrespect to attractiveness or repellency of the mosquito, Aedes aegypti.The graph indicated by reference numeral 150a is for air. The graphindicated by reference numeral 145a is for ISOCYCLOGERANIOL. The graphindicated by reference numeral 176a is for FLORALOL. The "X" axis alongwhich the particular materials are measured insofar as theirattractiveness or repellency is concerned is indicated by referencenumeral 107. The number of insects collected per interval is indicatedon the "Y" axis and the "Y" axis is indicated by reference numeral 100.The results are tabulated in Table I(A) as follows:

                  TABLE I(A)                                                      ______________________________________                                        Composition                                                                            Graph                                                                Tested   No.       Insects Collected per Interval                             ______________________________________                                        ISOCYCLO-                                                                              145a       4      1    0    0    0    3                              GERANIOL                                                                      Air      150a      555    512  552  552  574  494                             FLORALOL 176a       3      1    0    0    0    0                              ______________________________________                                    

FIG. 1B is a series of graphs depicted in three-dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of air, ISOCYCLOGERANIOL and FLORALOL withreference to attractiveness or repellency for Aedes aegypti. The graphsare based on experiments run for a period of six hours with sixintervals of one hour each. The graph indicated by reference numeral145b is for ISOCYCLOGERANIOL. The graph indicated by reference numeral150b is for air. The graph indicated by reference numeral 176b is forFLORALOL. The results are tabulated in Table I(B) as follows:

                  TABLE I(B)                                                      ______________________________________                                        Composition                                                                            Graph                                                                Tested   No.       Insects Collected per Interval                             ______________________________________                                        ISOCYCLO-                                                                              145b       3      0    2    5    4    0                              GERANIOL                                                                      Air      150b      494    547  580  566  559  533                             FLORALOL 176b       0      5    1    4    2    0                              ______________________________________                                    

FIG. 2A is a ,series of graphs depicted in three-dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of the materials:

(i) air;

(ii) ISOCYCLOGERANIOL having the structure: ##STR52## (iii) FLORALATEhaving the structure: ##STR53## (iv) DIHYDROFLORALOL having thestructure: ##STR54## The test data is for the mosquitoes, Aedes aegypti.The graphs are based on experiments run for a period of one hour withsix intervals of ten minutes each. The graph indicated by the referencenumeral 200a is for air. The graph indicated by reference numeral 205ais for ISOCYCLOGERANIOL. The graph indicated by reference numeral 203ais for FLORALATE. The graph indicated by reference numeral 202a is forDIHYDROFLORALOL. The results are tabulated in Table II(A) as follows:

                  TABLE II(A)                                                     ______________________________________                                        Composition                                                                             Graph                                                               Tested    No.     Insects Collected per Interval                              ______________________________________                                        Air       200a    393    494  570  554  584  578                              ISOCYCLO- 205a     0      0    0    0    0    0                               GERANIOL                                                                      FLORALATE 203a     1      22   0    24   7    27                              DIHYDRO-  202a     0      0    0    0    0    0                               FLORALOL                                                                      ______________________________________                                    

FIG. 2B is a series of graphs depicted in three-dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of the materials:

(i) air;

(ii) ISOCYCLOGERANIOL having the structure: ##STR55## (iii) FLORALATEhaving the structure: ##STR56## (iv) DIHYDROFLORALOL having thestructure: ##STR57## The graphs are based on experiments run for aperiod of eighteen hours with six intervals of three hours each using asthe insect to be tested the mosquito, Aedes aegypti. The graph indicatedby reference numeral 200b is for air. The graph indicated by referencenumeral 205b is for ISOCYCLOGERANIOL. The graph indicated by referencenumeral 203b is for FLORALATE. The graph indicated by reference numeral202b is for DIHYDROFLORALOL. The results are tabulated in Table II (B)as follows:

                  TABLE II(B)                                                     ______________________________________                                        Composition                                                                             Graph                                                               Tested    No.       Insects Collected per Interval                            ______________________________________                                        Air       200b      4472   3833 5026 4108 716  0                              ISOCYCLO- 205b        7      6   50   134  0   0                              GERANIOL                                                                      FLORALATE 203b       19      7    0    0   0   0                              DIHYDRO-  202b        1      2    0    1   0   0                              FLORALOL                                                                      ______________________________________                                    

FIG. 3 is a series of graphs depicted in three-dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of the materials:

(i) air; and

(ii) DIHYDROFLORALOL having the structure: ##STR58## The graphs arebased on experiments run for a period of one hour with six intervals often minutes each using as the insect to be tested the Horn fly(Haematobia irritans [L.]). The graph indicated by reference numeral 300is for air. The graph indicated by reference numeral 302 is forDIHYDROFLORALOL. The results are tabulated in Table III as follows:

                  TABLE III                                                       ______________________________________                                        Composition                                                                            Graph                                                                Tested   No.       Insects Collected per Interval                             ______________________________________                                        Air      300       1712   302  257  260  281  164                             DIHYDRO- 302        22     3    23   1    0    1                              FLORALOL                                                                      ______________________________________                                    

FIG. 4 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of the materials:

(i) air;

(ii) ISOCYCLOGERANIOL having the structure: ##STR59## (iii) FLORALATEhaving the structure: ##STR60## (iv) FLORALOL having the structure:##STR61##

The graphs are based on experiments run for a period of one hour withsix intervals of ten minutes each using as the insect to be tested theHorn fly (Haematobia irritans [L.]). The graph indicated by referencenumeral 400 is for air. The graph indicated by reference numeral 445 isfor ISOCYCLOGERANIOL. The graph indicated by reference numeral 443 isfor FLORALATE. The graph indicated by reference numeral 426 is forFLORALOL. The results are tabulated in Table IV as follows:

                  TABLE IV                                                        ______________________________________                                        Composition                                                                             Graph                                                               Tested    No.     Insects Collected per Interval                              ______________________________________                                        Air       400     170    198  304  339  229  346                              ISOCYCLO- 445      0      0    0    0    0    0                               GERANIOL                                                                      FLORALATE 443      1      5    0    0    1    0                               FLORALOL  426      0      0    0    0    0    0                               ______________________________________                                    

FIG. 5 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of the materials:

(i) air;

(ii) CAMEKOL DH having the structure: ##STR62## (iii) FLORALOL havingthe structure: ##STR63## (iv) DIHYDROFLORALOL having the structure:##STR64##

The graphs are based on experiments run for a period of one hour withsix intervals of ten minutes each using as the insect to be tested theHorn fly (Haematobia irritans [L.]).

The graph indicated by reference numeral 500 is for air. The graphindicated by reference numeral 536 is for CAMEKOL DH. The graphindicated by reference numeral 526 is for FLORALOL. The graph indicatedby reference numeral 542 is for DIHYDROFLORALOL. The results aretabulated in Table V as follows:

                  TABLE V                                                         ______________________________________                                        Composition                                                                              Graph                                                              Tested     No.       Insects Collected per Interval                           ______________________________________                                        CAMEKOL DH 536       1     1   0    0     1    0                              Air        500       1     5   73   170   43   8                              FLORALOL   526       4     1   1    0     0    0                              DIHYDRO-   542       0     6   0    1     0    0                              FLORALOL                                                                      ______________________________________                                    

FIG. 6 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of the materials:

(i) Air;

(ii) FLORALATE having the structure: ##STR65## (iii) DIHYDROFLORALOLhaving the structure: ##STR66##

The graphs are based on experiments run for a period of one hour withsix intervals of ten minutes each using as the insect to be tested thehouse fly (Musca domestica L.(Diptera:Muscidae)). The graph indicated byreference numeral 643 is for FLORALATE. The graph indicated by referencenumeral 600 is for air. The graph indicated by reference numeral 642 isfor DIHYDROFLORALOL. The results are tabulated in Table VI as follows:

                  TABLE VI                                                        ______________________________________                                        Composition                                                                             Graph                                                               Tested    No.       Insects Collected per Interval                            ______________________________________                                        FLORALATE 643       0     3    0     0   0    2                               Air       600       0     62   1     1   1    19                              DIHYDRO-  642       0     6    3     0   2    7                               FLORALOL                                                                      ______________________________________                                    

FIG. 7 is a series of graphs depicted in three dimensions (in arectangular mode for the "X" and "Y" axes) showing the relativeattractiveness or repellency of the materials:

(i) FLORALOL having the structure: ##STR67## (ii) Air.

The graphs are based on experiments run for a period of one hour withsix intervals of ten minutes each using as the insect to be tested thehouse fly, Musca domestica L.(Diptera:Muscidae). The graph indicated byreference numeral 700 is for air. The graph indicated by referencenumeral 726 is for FLORALOL. The results are tabulated in Table VII asfollows:

                  TABLE VII                                                       ______________________________________                                        Composition                                                                            Graph                                                                Tested   No.       Insects Collected per Interval                             ______________________________________                                        FLORALOL 726       2        8  0     3   0   0                                Air      700       172     17  0     2   0   0                                ______________________________________                                    

FIG. 8A is a graph showing the mean number of mosquitoes collected (onthe "Y" axis) versus the treatment substance (on the "X" axis) using thefield trap of FIG. 21 having six ports and three infra-red lightemitting diodes and using the following materials:

(i) a 50:50 mole:mole mixture of air and carbon dioxide with the feedrate of carbon dioxide being 2.7 gram moles per hour;

(ii) CAMEKOL DH having the structure: ##STR68## (iii) ISOCYCLOGERANIOLhaving the structure: ##STR69##

The bar graph showing the mean number of insects collected using themixture of air and carbon dioxide is indicated by reference numeral8000a. The bar graph indicating the mean number of mosquitoes collectedusing CAMEKOL DH is indicated by reference number 8036a. The bar graphusing ISOCYCLOGERANIOL is indicated by reference numeral 8045a.

FIG. 8B is a series of bar graphs showing the mean number of mosquitoescollected on the "Y" axis versus the treatment substance on the "X" axisusing the semiochemical field trap of FIG. 21 having six ports withthree infra-red light emitting diodes. The substances used are:

(i) a 50:50 mixture of air and carbon dioxide with the carbon dioxiderate being 2.7 gram moles per hour;

(ii) DIHYDROFLORALOL having the structure: ##STR70## (iii)ISOCYCLOGERANIOL having the structure: ##STR71## (iv) ISOCYCLOGERANIOLmethyl carbonate having the structure: ##STR72## (v) ISOCYCLOGERANIOLethyl carbonate having the structure: ##STR73## The bar graph showingthe mean number of mosquitoes collected using the mixture of air andcarbon dioxide is indicated by reference numeral 8000b. The bar graphusing the DIHYDROFLORALOL is indicated by reference numeral 8042b. Thebar graph showing the results using ISOCYCLOGERANIOL is indicated byreference numeral 8045b. The bar graph showing the results when usingthe ISOCYCLOGERANIOL methyl carbonate is indicated by reference numeral8003b. The bar graph showing the results using the ISOCYCLOGERANIOLethyl carbonate is indicated by reference numeral 8004b.

FIG. 8C is a series of bar graphs indicating the mean number ofmosquitoes trapped on the "Y" axis versus the treatment substance on the"X" axis using a semiochemical field trap as illustrated in FIG. 21having six ports with three infra-red light emitting diodes using thefollowing substances:

(i) a mixture of air and carbon dioxide in a mole ratio of 50:50 at arate of carbon dioxide of 2.7 gram moles per hour;

(ii) FLORALOL having the structure: ##STR74## (iii) FLORALATE having thestructure: ##STR75##

The bar graph showing the results using the mixture of air and carbondioxide is indicated by reference numeral 8000c. The bar graph showingthe results using FLORALOL is indicated by reference numeral 8026c. Thebar graph showing the results using FLORALATE is indicated by referencenumeral 8043c.

In each of the experiments, the results for which are shown in FIGS. 8A,8B and 8C the following insects were shown to be either repelled orattracted:

Culex nigripalpus;

Aedes atlanticus;

Culex salinarius;

Aedes vexans;

Culex spp.;

Simulium spp.;

Psoroferia ferox;

Aedes infirmatus;

Drosophila melanogaster;

Coccinellidae;

Anopheles crucians;

Psoroferia columbiae;

Culicoides spp.; and

Aedes spp.

In referring to the extruder of FIG. 9, polymer 12 and 13 is admixed invessel 14 and added at barrel segment S-1 of barrel 16 to the extruderwhich is powered by motor 15 held in place by bracket 23A.Simultaneously into barrel segment S-6 (one of segments 18a, 18b, 18c or18d) is added the insect repellent which is one or more of the dimethylsubstituted oxymethyl cyclohexane derivatives and/or geranial-containingcompositions of our invention previously held in container 17. Therepellent/perfumant mixture is pumped through pump 23 into barrelsegment 18c/S-6. Simultaneously, foaming agent is added from vessel 19into barrel segment S-8 from barrel segment S-10, a foamed towcontaining polymer having imbedded therein insect repellent/perfume ispassed through cooling bath 20 and the cooled tow 22 is then passed intomascerating machine 21 wherein the tow is chopped into particles andheld in container 21a for future use, e.g., for use in conjunction withthe manufacture of the insect repellent soap or detergent bars describedin detail, infra.

Referring to FIGS. 11-20, inclusive, a preferred embodiment of ourinvention comprises an ellipsoidally shaped detergent tablet 830. Apreferred embodiment of our invention comprises an ellipsoidally-shapeddetergent tablet 830 containing a solid plastic core 832 which can befabricated from, for example, polyethylene, polypropylene, nylon, abiodegradable polymer such as poly(epsilon caprolactone) or any polymercapable of having therein microvoids from which an insectrepelling/perfuming substance, e.g., at least one of the appropriatedimethyl substituted oxymethyl cyclohexane derivative-containing orgeranial-containing compositions of our invention will be controllablytransported from the plastic core into and through the soap cake over areasonable period of time during the use of the soap cake. Such polymerscan be microporous polymers, such as those described in U.S. Pat. No.4,247,498 issued on Jan. 27, 1981, the specification for which isincorporated herein by reference. Surrounding the central plastic corecontaining insect repellent 832, is detergent 830' which is in the solidphase at ambient conditions, e.g., room temperature and atmosphericpressure. Examples of workable detergents 830' are "elastic" detergentssuch as those described in U.S. Pat. No. 4,181,632 issued on Jan. 1,1980, the disclosure of which is incorporated herein by reference, or"transparent" soaps such as those set forth in U.S. Pat. No. 4,165,293issued on Aug. 21, 1979, the disclosure of which is incorporated hereinby reference. Other examples of the detergent 830' useful in ourinvention are those set forth as "variegated soaps" in Canadian LettersPatent No. 1,101,165 issued on May 19, 1981.

On use of the soap tablet 830 or detergent bar, the insect repellentagent originally located in plastic core 832 is transported at a steadystate from core 832 through core surface 831 through the detergent 830'and finally through the surface of the detergent bar at, for example,833, 834, 835 and 836.

The detergent bar or tablet 830 of our invention may be of any geometricshape, for example, a rectangular parallelepiped tablet as is shown inFIGS. 15, 16 and 17 containing solid plastic core 839. The insectrepellent located in solid plastic core 839 on use of the detergent barpasses through at steady state, surface 837 of FIG. 16, detergent 838and finally surface 839 at, for example, locations 840, 841, 842 and843. The environment surrounding the detergent bar on use thereof isthen treated with the insect repellent at 843, 844 and 845, for example.Optionally, aromatizing agent can also be contained in the detergent bar(if desired) and so the environment surrounding the detergent bar on usethereof would also be aesthetically aromatized at 843, 844 and 845, forexample, if the appropriate dimethyl substituted oxymethyl cyclohexanederivative-containing and/or geranial-containing composition of ourinvention is insufficient for such aromatization. In certain instancessuch appropriate dimethyl substituted oxymethyl cyclohexanederivative-containing or geranial-containing compositions are indeedsufficient for such aromatization.

As is shown in FIGS. 18, 19 and 20 the plastic core of the detergenttablet 830 may have a single finite void at its center 851 (of FIGS. 19and 20) in which the insect repellent agent and optionally anyadditional aromatizing agents are contained. The plastic core is a shell848 having outer surface 852 (shown optionally any additionalaromatizing agent) contained in the void in the plastic core permeatesthrough shell 848, past surfce 852 at a steady state, through thedetergent 847 and to the environment at, for example, 856,857 858 and859.

In addition to the insect repellent contained in the core, e.g., core839 or core void the core can also contain other materials fortherapeutic use, for example, bacteriastats, deodorizing agents and thelike which are compatible with the appropriate dimethyl substitutedoxymethyl cyclohexane derivative-containing and/or geranial-containingcompositions of our invention. In the alternative, the plastic core ofthe detergent tablet of FIGS. 18, 19 and 20 may have an empty singlefinite void at its center 851 with the insect repellent contained in theshell 848.

At the end of the use of the detergent tablet, the hollow core or thesolid core can be used as an insect repelling and aroma imparting or airfreshener household article. In addition, depending on the ratio of thevolume of the void 851, to the solid part of the detergent tablet ofFIGS. 18, 19 and 20, the detergent tablet of FIGS. 18, 19 and 20 can beso fabricated that it will float on the surface of the liquid in whichit is being used and this physical attribute has certain obviousadvantages.

FIG. 22 is a series of bar graphs showing the feeding contact for a meanfeeding contact for a mean one hour feeding contact period of time usingthe olfactometer apparatus of FIG. 10. The number of feeding contactsare set forth on the "Y" axis and the treatment substance is set forthon the "X" axis. The bar graph indicated by reference numeral 2200 isfor air and shows the results using said air. The bar graph indicated byreference numeral 2243 shows the results using FLORALATE having thestructure: ##STR76##

The bar graph indicated by reference numeral 2244 shows the resultsusing geranial having the structure: ##STR77##

FIG. 23 is a series of bar graphs showing on the "Y" axis the mean 2-6hour number of feeding contacts for mosquitoes Aedes aegypti using theolfactometer of FIG. 10 versus the treatment substance on the "X" axis.The graph indicated by reference numeral 2300 is the graph showing theresults using air. The graph indicated by reference numeral 2343 is thebar graph showing the results using FLORALATE having the structure:##STR78## The graph indicated by reference numeral 2344 is the bar graphshowing the results of this experiment using geranial having thestructure: ##STR79##

The apparatus of FIG. 10 is disclosed in detail in U.S. Pat. No.5,134,892 the specification for which is incorporated herein byreference.

The following examples are illustrative and the instant patentapplication is intended to be restricted only to the scope of the claimsand not to the examples.

EXAMPLE I

A transparent candle base mixture is produced by intimately admixing thefollowing ingredients:

    ______________________________________                                        Ingredients      Parts by Weight                                              ______________________________________                                        VERSAMID ® 1635                                                                            34.0                                                         Barlol 12C2      51.0                                                         Butyl Stearate   3.5                                                          NEVEX ® 100  5.0                                                          SPAN ®       1.5                                                          Isopropyl Isostearate                                                                          4.0                                                          Isopropyl Myristate                                                                            4.0                                                          ______________________________________                                    

The foregoing mixture is placed in an autoclave and intimately admixedwith 22% by weight of the entire mixture of a perfuming-insect repellentcomposition containing the following ingredients:

    ______________________________________                                        Ingredients         Parts by weight                                           ______________________________________                                        ISOCYCLOGERANIOL having                                                       the structure:                                                                 ##STR80##          25                                                        FLORALATE having                                                              the structure:                                                                 ##STR81##          25                                                        Geranial having the                                                           structure:                                                                     ##STR82##          25                                                        CAMEKOL DH having                                                             the structure:                                                                 ##STR83##          25                                                        ______________________________________                                    

The autoclave is sealed and heated to 180° C. under 25 atmospherespressure and maintained with vigorous shaking for a period of fivehours. At the end of the five hour period, the autoclave isdepressurized (being under a nitrogen pressure atmosphere) and theautoclave is opened and the contents are then poured into cylindricalcandle molds 4" in height and 2" in diameter containing 0.125" wicks.The resulting candles have efficacious Aedes aegypti, Aedes albopictus,and Musca domestica L. repellencies and have aesthetically pleasingaromas on use.

The candles are effective in preventing house flies and the mosquitospecies Aedes aegypti and Aedes albopictus from entering a room in whichfour candles have been burning for 15 minutes, the said room havingdimensions of 6'×15'×15' and having a 2'×2' open portal adjacent to ahouse fly and mosquito-infested region in the month of August, 1992 inthe temperate zone of Highlands, N.J. adjacent Raritan Bay.

EXAMPLE II

A study was conducted to evaluate the efficacy of candles which aredesignated as "A", "B" and "C" in repelling house flies (Musca domesticaL.(Diptera:Muscidae) and the mosquito species Aedes aegypti and Aedesalbopictus.

Candle "A" contained 95% Paraffin Wax and 5% of ISOCYCLOGERANIOL ethylcarbonate having the structure: ##STR84##

Candle "B" contained 90% Paraffin Wax and 10% citronella oil.

Candle "C" contained only Paraffin Wax.

The candles are allowed to burn for 20 minutes and the number of houseflies (Musca domestica L.(Diptera:Muscidae)) and mosquitoes (Aedesaegypti and Aedes albopictus) repelled is recorded for the next 60minutes with the following equipment and procedure:

Materials Test Chamber

The evaluation was conducted in a 28.3 cubic meter chamber with airingports. A screened cage measuring 15 cm×15 cm×47.5 cm was attached insidean upper airing port, and a screened repellency observation cagemeasuring 15 cm×15 cm×32.5 cm was attached outside the upper airingport. The two cages were held together by a Masonite plate which fitfirmly in the airing port. A 4-cm hole located in the center of eachMasonite plate provided an escape for the test insects. A barrier wasused to close the hole.

Attractant

A caged grey mouse was used as an attractant and was placed inside thechamber in the larger section of the repellency cage.

Test Insects

(i) Adult House Flies (Musca domestica L.(Diptera:Muscidae));

(ii) Aedes aegypti mosquitoes;

(iii) Aedes albopictus mosquitoes are Test Insects.

Procedure

For each replicate, 75 to 100 adult house flies, 75 to 100 Aedes aegyptimosquitoes and 75 to 100 Aedes albopictus mosquitoes were removed fromthe rearing cage by means of a vacuum aspirator, and transferred bycarbon dioxide anesthesia to the inner cage containing the grey mouse.The assembled cage was placed in one of the upper ventilation ports ofthe chamber. For each experimental situation the test insects weretransferred to a clean cage containing the mouse. A candle containingthe insect repellent substance to be tested was placed centrally on thechamber floor and burned for 20 minutes before initiating the repellencycounts. The maximum period for the repellency counts was 60 minutes. Thefirst repellency count was made at 10 minutes after the burning ended,and subsequent counts were taken at 5-minute intervals thereafter. Thenumber of house flies, Aedes aegypti mosquitoes and Aedes albopictusmosquitoes repelled were those escaping to the outside cage. For thecontrol, counts were made in a similar manner, but no candle was burned.

The same three candles were used for all four replicates. Betweenreplicates the chamber was exhausted, the Kraft paper flooring for thechamber was replaced, and the two screened repellency cages weresubmerged in hot detergent water, rinsed and dried.

Results

The overall average percent of house flies, Aedes aegypti and Aedesalbopictus mosquitoes repelled for each candle for 60 minutes was asfollows:

Candle "A"--98%

Candle "B"--52%

Candle "C"--12%.

The repellency against the three species:

Musca domestica L. (Diptera:Muscidae);

Aedes aegypti; and

Aedes albopictus

were equivalent in this test.

What is claimed is:
 1. A method of repelling at least one member of the insect species: Musca domestica L. (Diptera:Muscida), Aedes aegypti, Culex nigripalpus, Aedes atlanticus, Culex salinarius, Aedes vexans, Culex spp., Simulium spp., Psoroferia ferox, Aedes infirmatus, Drosophila melanogaster, Coccinellidae, Anopheles crucians, Psoroferia columbiae, Culicoides spp., Aedes spp., Haematobia irritans [L.] and/or Aedes albopictus for a finite period of time from a three-dimensional space inhabited by said insect species member consisting essentially of the step of exposing said three-dimensional space to an effective insect species member-repelling concentration and quantity of a dimethyl substituted oxymethyl cyclohexene derivative-containing composition of matter defined according to the structure: ##STR85## wherein R₂ is methyl or hydrogen.
 2. The method of claim 1 wherein the insect repelling substance has the structure: ##STR86##
 3. The method of claim 1 wherein the insect repelling substance has the structure: ##STR87##
 4. The method of claim 1 wherein the insect repelling substance is contained in a polymer matrix.
 5. The method of claim 4 wherein the polymer matrix comprises a biodegradable polymer.
 6. The method of claim 5 wherein the biodegradable polymer is a polycaprolactone polymer or a polyurethane polymer.
 7. The method of claim 1 wherein the insect repelling composition is initially admixed with a soap base; the resulting mixture is formulated into a soap article; and the resulting soap article is used in a washing procedure on a living mammal, sufficiently to repel said insect species member.
 8. The method of claim 2 wherein the insect repellent-containing composition is initially admixed with a soap base; the resulting mixture is formulated into a soap article; and the resulting soap article is used in a washing procedure on a living mammal in a sufficient quantity to repel said insect species member.
 9. The method of claim 4 wherein the insect repellent-containing composition contained in the polymer matrix is formed into a core and the core is surrounded with a soap base; and the resulting article is applied in a washing procedure on a living mammal in a sufficient quantity to repel said insect species member. 